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Metal ions doped into merocyanine form of coumarin derivatives: nonlinear optical molecular switches

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Abstract

In the present study, DFT calculations are carried out on domestically designed 7-methyl-2-phenyl-5’H-spiro[chromene-4,2′-chromeno[3,4-e][1,3]oxazin]-5′-one spiropyran and merocyanine derivatives to recognize alkali and alkaline earth metal ions. Detection of these metal ions can be attained by exploiting the variation of the second-order nonlinear optical properties. Merocyanine forms of these derivatives exhibit the ability to complex with different metal ions (Li+, Na+, K+, and Ca2+), which is associated with large contrasts in the hyper-Rayleigh scattering (HRS) response as a function of metal size and charge. Interestingly, in this study, Mero-Li+ shows significant nonlinear optical response with dynamic HRS first hyperpolarizability amounting to 7607 a.u., which is about nine times higher than its corresponding spiro form (846 a.u.) at the CAM-B3LYP/6-311G* level of theory. The present investigation clarifies the effect of metal nature on the enhancement of the first hyperpolarizability between the closed and open forms of the studied coumarin derivatives.

The coumarin-based compound 3 demonstrate the higher second-order NLO responses as a function of metal cation size and charges. Complexation of smaller alkali metal ions leads to the formation of stronger metal-ligand bonds, larger geometrical relaxations and significant enhancement of the HRS first hyperpolarizabilities. This present investigation elucidates the effect of metal nature on the enhancement of the first hyperpolarizability between the closed and open forms of studied coumarin derivatives

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Acknowledgments

H-L Xu acknowledges support for the project funded by the China Postdoctoral Science Foundation (2014 M560227) and the Fundamental Research Funds for the Central Universities 2412018ZD008. S Muhamma d at the King Khalid University is thankful to the Deanship of Scientific Research at King Khalid University for funding this work through Research Group Project under grant number (R. G. P.1/165/40).

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  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, Jilin, People’s Republic of China

    Ali Muhammad Arif, Afifa Yousaf, Mansoor Akhtar, Hong-liang Xu & Zhong-Min Su

  2. Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, Jilin, People’s Republic of China

    Rong-Lin Zhong

  3. Department of Physics, College of Science, King Khalid University, P.O. Box 9004, Abha, 61413, Saudi Arabia

    Shabbir Muhammad

  4. School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun, Jilin, People’s Republic of China

    Zhong-Min Su

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  1. Ali Muhammad Arif
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Arif, A.M., Yousaf, A., Zhong, RL. et al. Metal ions doped into merocyanine form of coumarin derivatives: nonlinear optical molecular switches. J Mol Model 25, 212 (2019). https://doi.org/10.1007/s00894-019-4068-6

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